Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

doi:10.1007/s13659-022-00343-2

Natural Products and Bioprospecting ›› 2022, Vol. 12 ›› Issue (3): 20-20.DOI: 10.1007/s13659-022-00343-2

• SHORT COMMUNICATION • Previous Articles Next Articles

Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

Pablo A. Chacón-Morales¹, Juan M. Amaro-Luis¹, Luis Beltrán Rojas Fermín², Rémi Jacquet³, Denis Deffieux³, Laurent Pouységu³, Stéphane Quideau³

1 Natural Products Laboratory, Department of Chemistry, Faculty of Science, University of Los Andes, Mérida, 5101, Venezuela;
2 Research Institute, Faculty of Pharmacy and Bioanalysis, University of Los Andes, Mérida, 5101, Venezuela;
3 ISM (CNRS-UMR 5255), Univ. Bordeaux, 351 cours de la Libération, 33405, Talence Cedex, France

Received:2022-01-25 Online:2022-06-24 Published:2022-06-24
Contact: Pablo A. Chacón-Morales,E-mail:pablochacon1@gmail.com
Supported by:
This work was financially supported by the National Fund of Science, Technology and Innovation (FONACIT) (Grant N° 201300288) within the framework of the project PCP France-Venezuela and by the CDCHTA-ULA (Grant N° C-1935-15-08-ED). Thank are due to Eng. Juan Carmona Arzola, Department of Pharmacognosy and Organic Medicaments, Faculty of Pharmacy and Bioanalysis, University of Los Andes (ULA) for identification of plant material.

Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

Pablo A. Chacón-Morales¹, Juan M. Amaro-Luis¹, Luis Beltrán Rojas Fermín², Rémi Jacquet³, Denis Deffieux³, Laurent Pouységu³, Stéphane Quideau³

1 Natural Products Laboratory, Department of Chemistry, Faculty of Science, University of Los Andes, Mérida, 5101, Venezuela;
2 Research Institute, Faculty of Pharmacy and Bioanalysis, University of Los Andes, Mérida, 5101, Venezuela;
3 ISM (CNRS-UMR 5255), Univ. Bordeaux, 351 cours de la Libération, 33405, Talence Cedex, France

通讯作者: Pablo A. Chacón-Morales,E-mail:pablochacon1@gmail.com
基金资助:
This work was financially supported by the National Fund of Science, Technology and Innovation (FONACIT) (Grant N° 201300288) within the framework of the project PCP France-Venezuela and by the CDCHTA-ULA (Grant N° C-1935-15-08-ED). Thank are due to Eng. Juan Carmona Arzola, Department of Pharmacognosy and Organic Medicaments, Faculty of Pharmacy and Bioanalysis, University of Los Andes (ULA) for identification of plant material.

Abstract

Abstract: From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1. The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the substrate yielding the 2-oxoaustroeupatol (2) and 2,19-dioxoaustroeupatol (3). The treatment of 2 with sodium periodate yields a heterocyclic derivative (ε-caprolactone derivate 4) formed by oxidative cleavage and unexpected intramolecular attack of the hydroxymethylene (C-19) oxygen to the ketonic carbon (C-2). A plausible mechanistic pathway for the obtention of compound 4 is proposed.

Key words: Oxidative cleavage, Austroeupatol, NaIO₄, IBX, Lactonization, NMR

摘要： From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1. The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the substrate yielding the 2-oxoaustroeupatol (2) and 2,19-dioxoaustroeupatol (3). The treatment of 2 with sodium periodate yields a heterocyclic derivative (ε-caprolactone derivate 4) formed by oxidative cleavage and unexpected intramolecular attack of the hydroxymethylene (C-19) oxygen to the ketonic carbon (C-2). A plausible mechanistic pathway for the obtention of compound 4 is proposed.

关键词: Oxidative cleavage, Austroeupatol, NaIO₄, IBX, Lactonization, NMR

Pablo A. Chacón-Morales, Juan M. Amaro-Luis, Luis Beltrán Rojas Fermín, Rémi Jacquet, Denis Deffieux, Laurent Pouységu, Stéphane Quideau. Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol[J]. Natural Products and Bioprospecting, 2022, 12(3): 20-20.

[1]	Yi-Yun Yuan, Yan Li, Wen-Yu Lu, Ai-Lin Liang, Jing Li, Wen-Xuan Wang. Xylariaides A and B, novel cytochalasans with a unique 5/6/5/3 ring system from a soil fungus Xylaria sp. Y01 [J]. Natural Products and Bioprospecting, 2025, 15(3): 23-23.
[2]	Shuruq Alsuhaymi, Upendra Singh, Inas Al-Younis, Najeh M. Kharbatia, Ali Haneef, Kousik Chandra, Manel Dhahri, Mohammed A. Assiri, Abdul-Hamid Emwas, Mariusz Jaremko. Untargeted metabolomics analysis of four date palm (Phoenix dactylifera L.) cultivars using MS and NMR [J]. Natural Products and Bioprospecting, 2023, 13(6): 44-44.
[3]	Elier Galarraga, Andersson Mavares, Neudo Urdaneta, Rafael E. Rodríguez-Lugo, Juan Manuel Amaro-Luis. Artificial Triterpenoid Fatty Acid Ester Isolated From the Leaves of Phytolacca icosandra L [J]. Natural Products and Bioprospecting, 2020, 10(4): 221-225.
[4]	Dezhi Yang, Bin Su, Yancai Bi, Li Zhang, Baoxi Zhang, Junke Song, Yang Lu, Guanhua Du. Preparation and Certification of a New Salvianolic Acid A Reference Material for Food and Drug Research [J]. Natural Products and Bioprospecting, 2020, 10(2): 67-76.
[5]	Hai-Li Yu, Qin Long, Wen-Fang Yi, Bao-Jia Yang, Yu Song, Xiao Ding, Shun-Lin Li, Xiao-Jiang Hao. Two New C21 Steroidal Glycosides from the Roots of Cynanchum paniculatum [J]. Natural Products and Bioprospecting, 2019, 9(3): 209-214.
[6]	Hou-Chao Xu, Kun Hu, Han-Dong Sun, Pema-Tenzin Puno. Four 14(13→12)-Abeolanostane Triterpenoids with 6/6/5/6-Fused Ring System from the Roots of Kadsura coccinea [J]. Natural Products and Bioprospecting, 2019, 9(3): 165-173.
[7]	S. Manimaran, K. SambathKumar, R. Gayathri, K. Raja, N. Rajkamal, M. Venkatachalapathy, G. Ravichandran, C. Lourdu EdisonRaj. Medicinal Plant Using Ground State Stabilization of Natural Antioxidant Curcumin by Keto-Enol Tautomerisation [J]. Natural Products and Bioprospecting, 2018, 8(5): 369-390.
[8]	Gao-Wei Li, Han Liu, Feng Qiu, Xiao-Juan Wang, Xin-Xiang Lei. Residual Dipolar Couplings in Structure Determination of Natural Products [J]. Natural Products and Bioprospecting, 2018, 8(4): 279-295.
[9]	Liang-Yan Liu, Han Sun, Christian Griesinger, Ji-Kai Liu. The Use of a Combination of RDC and Chiroptical Spectroscopy for Determination of the Absolute Configuration of Fusariumin A from the Fungus Fusarium sp [J]. Natural Products and Bioprospecting, 2016, 6(1): 41-48.
[10]	Marie Pascaline Rahelivao, Margit Gruner, Hanta Andriamanantoanina, Ingmar Bauer, Hans-Joachim Knölker. Brown Algae(Phaeophyceae) from the Coast of Madagascar:preliminary Bioactivity Studies and Isolation of Natural Products [J]. Natural Products and Bioprospecting, 2015, 5(5): 223-235.
[11]	Alan Rodrigues Teixeira MACHADO, Gisele Avelar LAGE, Felipe da Silva MEDEIROS, José Dias de Souza FILHO, Lúcia Pinheiro Santos PIMENTA. Quantitative analysis of trigonelline in some Annona species by proton NMR spectroscopy [J]. Natural Products and Bioprospecting, 2013, 3(4): 158-160.

Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

Preparation of a ε-caprolactonic diterpenoid derivate by unexpected oxidative cleavage/lactonization of 2-oxoaustroeupatol

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 11

Recommended Articles

Metrics

Comments